Packaging unit and process for making same



y 1951 M. M. SHIHADEH PACKAGING UNIT AND'PROCESS FOR MAKING SAME Filed Jan. 29, 1960 MUSA M. SH\HADEH LOW DENSITY COMPONENT HIGH -DENSITV COMPONENT COMPONENT a COMPONENT COMPONENT IN V EN TOR.

BY f W W AGENT 12,982,39 PACKAGING Algll) PROCESS FOR MAKING Musa M. stand, 267 Dan st, Brooklyn 17, NY. Filed Jan. 29, 19 0, Ser. No. 5,539 24 Claims. 01. 206 -47) My present invention relates to a single-container packaging unit for a plurality of chemically reactive components, and to "a process for making such units.

Multi-component'chemical systems and, more particularly, systems wherein at least two components (e.g.

polymerizable compounds and theiractivators) are adapted to interact upon suitable agitation to obtain a desired end product, have hither-to required the individual packaging of each reactivecomponent or, with joint storage, the physical separation-of the components by means of a removable barrier to avoid premature formation of the end product.

to be combined prior to use, wherein the disadvantages of handling a plurality of containers are obviated. p

According to a feature of the invention, a miscible barrier layer not requiring subsequent removal is interposed betweenmasses of chemically reactive materials in a single container. The barrier is designed to be relatively inert to attack by either reactive constituent adjacent thereto and-to-be impermeable by same while, how- I ever, being chemically compatible with the mixture resulting from the combination of the components between WhiCh'itfiS sandwiched, I havefound that this interposed,

ture, a refi-actory material designed to enhance fire-retarding properties, a viscosity modifier, a drying inhibitor or accelerator, or ;a substance capable of modifying the structural strength of the mixture or imparting thixotropic properties thereto. i

I have found further that a substantially inert and impermeable barrierof the character described, adapted to resist the difiusion of either reactive component into the other for relatively long periods while permitting the entire contents of the one-package system including the barrier to be stirred into a substantially homogeneous and compatible mixture, may include as its major constituent one or more of the following: drying and non-drying oils, varnishes, alkyds and derivatives thereof, waxes, gels, petroleum and coal-tar derivatives, as well as glyools, polyols,

2,982,396 Patented May 2, 1961 Itha nes and polyisocyanates, polyalkylene polysulfides,

chlorosulfonated polyethylenes, vulcanizable elastomers and halogenated derivatives thereof, and unsaturated polyesters; and, on the other hand, the activators, catalysts,

'vu-lcanizers and driers for these substances.

According to another feature of the invention the container is initially charged with one reactive component and subsequently with the barrier composition which forms a layer above the previously introduced reactive component. The other reactive component, adapted to com- :bine chemically with the first one upon the agitation of the contents of the container, is then deposited upon the barrier layer which physically separates the two components. To diminish the risk of intermixing the reactive components when charging the container, the less dense reactive component (generally theactivator or catalyst) is preferably deposited on' the barrier layer while the denser reactive component (generally the polymerizable substance or base) is positioned therebelow, particularly if the barrier composition is a liquid. It then advantageously should be selected to have a viscosity and a density intermediate those of the reactive components between which it is sandwiched. Alternatively the barrier layer may be of a thixotropic nature, partially solidifying upon introduction to the container, or a substance which has a relatively low melting point and is, therefore, solid at the storing ambient temperature. Since the reaction between components is generally exothermic, the temperature of the contents of the container may be raised sufliciently abovethe melting point of the barrier layer upon the introduction, for example, of the mixing paddle into the batch. The layer, thus raised above the melting point and ma liquid state, may then be stirred into the component mixture as previously mentioned. Moreover, the barrier layer may also be a super-cooled liquid or a gel. Similarly; the frictional heat of mixing may be suflicient to the following examples, wherein the parts referred to are on a weight basis. The examples will be more readily understood with reference to the accompanying drawing,

in which Figs. 1 and 2 show one-container packaging systems according to the invention with two and three components respectively.

More particularly, Fig. 1 shows a container 10 charged with an upper component A of low density, a lower component B of high density and an intervening barrier layer.

Example I Component A: Parts Activator (polyamide ,resin) Barrier C: I V

' Non-drying alkyd 20 Carbon black 7 7 Component B:

Epoxy resin Silica 70 Bary'tes 50 Component B, comprising a liquid epoxy resin formed by any diepoxy reaction between a polyhydroxy compound and either epichlorohydrin or dichlorohydrin, is

fatty acids and their derivatives. This barrier may be merized or partially polymerized epoxy resins, polynre-' formed by mixing the epoxy resin with commercially available silica and baryte extenders in the proportions shown. A suitable epoxy resin having an epoxide equivalent of to 290 (molecular weight per epoxy group), an average molecular weight of 340 to 450, and a viscos- -ity of 500t o 35000 cps. is manufactured by the Shell Chemical Company under the trade name Epon. The extenders, having particle sizes ranging between 40 and 325 mesh, are uniformly dispersed throughout the liquid epoxy resin. The component B is introduced into thecontainer 10, shown in the figure, forming a mass upon which the barrier C is deposited.

The barrier C comprises a non-drying alkyd of the type marketed under the name Paraplex G-20 by Rohm and Haas Co. The alkyd is 100% unmodified and has an acid number of 10 to 20, weighing between 0.97 and 1.1 kg. per liter. A pigmentatious material such as carbon'black is dispersed in a heated portion of the alkyd and ground to a fineness of approximately 5 to 6 on the Hegeman scale. Atop the barrier C I deposit a polyamide resin adapted to polymerize the epoxy resin of component B when the contents of the container are mixed. The polyarnide resin, forming component A, advantageously has an amine value ranging between 210 and 320(milligrams of potassium hydroxide equivalent to the base content of 1 gm. of polyamide, as determined bytitrationwith HCl) and a viscosity ranging between 2,000 to 6,000 cps.

Example 11 Components Aand B:

As in Example I Barrier C:

Coal-tar derivative ..parts 20 Titanium dioxide do 7 A barrier layer comprising a polymeric coal-tar derivative is interposed between the previously described components A and B. The barrier C, advantageously containing a titanium-dioxide pigment of the type marketed under the name Titanox Ranc dispersed in the coal-tar derivative, is treated as described with referenceto'Example I. A suitable coal-tar derivative is the-mixture of polynuclear aromatic hydrocarbons 'having a melting point less than 5 C., a flash point between'140 and 175 C., a viscosity in the range of from 295 to 4000 cps. at 25 C., and a specific gravity of 1.05, available under the name Transphalt from the Pennsylvania Industrial Chemical Corp.

Example Ill Components A and B:

As in Example I Barrier C:

Chlorinated wax 'parts 20 Pigment do 3 to7 A barrier comprising chlorinated paraffin compounds and a pigment (either carbon black'or titanium dioxide) is used in place of thebarriers previously described in Examples I and II. The chlorinated paratfin compounds, having a chlorine content ranging'between'40% and 72% an average molecillar weight between 570 and'1060 and a melting point'below 95 C., have a viscosity ranging from 20 poises to solid at normal room temperature. Some of these compounds must be heated above their melting points to permit the barrier composition to be poured into the container. Since the barrier-will besubstantially solid at room temperature, it will possess great mechanical strength prior to stirring and render the packaging system stable for long periods. The heat evolved in the exothermic reaction between components A and B is generally suflicient to melt the barrier and to permit the mixing of the contents into a homogeneous mass.

Example IV Components A and B:

As in Example I 4 Barrier C:

Chlorinated polyphenyls 20 parts. Pigments as required.

35 to 850 saybolts at about 52 C.), a density of 1.182

to 1.650 at 25 C., andranging from 54% to 68% of chlorination.

Example V Components A and B:

As in Example I Barrier C:

Terpene polymers 20 parts. Pigments as required.

I have found thatterpene polymers and mixtures thereof, having a' melting range from 10 to 70 C., are also satisfactory barriers between components A and 'B of Example I. Terpene polymers having molecular weights below 1100, acid numbers less than 4 and saponification numbersless than 4 are available from the Pennsylvania Industrial Chemical Company under the name Piccolyte.

Example VI Components A and B:

As in Example I Barrier C:

Petrolatum 20 parts. Pigments as required.

The barrier between the components Aand B includes as a major constituent, petrolatum, a semi-solid fraction of the petroleum refining process-at storage temperatures. The petrolatum, commonly referred to aspetroleum jelly, requires heating and melting tofacilitate its application.

Example VII Components A and B:

As in Example I Barrier C:

Chlorinated wax 10 parts. Microcrystalline wax 10 parts. Pigments as required.

Microcrystalline wax, a-product extracted from refinery still residues and comprising moleculeshaving approximately 41 to '50 carbon atoms, has a melting rangefrom 55 to 75 C. The-microcrystalline wax is mixed with chlorinated wax (previously described) -a.nd pigment in the proportions shown -at a temperature sufficiently high The liquid barrier mixture is divided into two portions, one

'of which is poured over thecomponent 'Bpreviously introduced into the container. The composition is permitted to cool and solidify, whereupon the second portion is poured onto the solidified surface to'fill 'anygapstherein and to'sealcompletely the component B from any contact with the activator (component A) which is poured onto the now solidified barrier. There is no danger, therefore, that cracks or gaps in a solid barrier layer will permit even a trickle of activator topercolate through and contact the epoxy base in component B. A similar technique may be used, if necessary, wherever the barrier comprises a substance which is a solid or-semi-solid at storage temperatures. 7

Example VIII Components-A and B:

As in Example I Barrier C:

30% solution ofcellulose .acetobutyrate /2 sec 30 parts. Pigments As required.

A 30% solution of cellulose acetobutyrate-% sec. in

acetate ester has also been found to be an effective barrier in combination with pigmentatious material, or in the absence-thereof, between the components A and B.

Component B comprises as a major constituent prepolymers of urethane (e.g. Solithin 113" of the Thiokol Chemical Co.) having isocyanate reactive terminals and I adapted to form a curable polymer with the major active constituent of component A, ricinoleyl alcohol. Whiting and silica serve as extender fillers and pigments, and are ground in vehicles such as tributyl phosphate (component A), the plasticizer (component B) and the barrier sub stance. The barrier, interposed between the two components as previously described as, for instance, in Example I, comprises a compound resulting from epoxy esterification reactions and present in xylol solution. A

suitable solution having 70% solids (epoxy ester) is marketed by Jones-Dabney and Co. under the name Epi- Tex 131 1.

Example IX 1 Component A: Parts Ricinus oil 100 Whiting 100 Colloidal silica I Barrier C:

Piccopale resin .r 20 Whiting v 50 Component B:

Polyisocyanate 100 Whiting 50 Colloidal silica Plasticizer (e.g. tributyl phosphate) Piccopale is a hydrocarbon resin produced by the polymerization of unsaturated compounds resulting from a petroleum-refining process, having a softening point between 65 and 90 C. The barrier of this example is formed by grinding the pigment (whiting) in the warmed resin. The barrier may be added to the container as described in Example VII, to separate the polyisocyanate from the ricinus oil (castor oil) adapted to react therewith.

Similarly, the barrier of Example X may comprise halogenated (e.g. chlorinated) wax, halogenated polyphenyls, terpene polymers, non-drying alkyds and coaltar derivatives, all previously described.

An organic polysulfide base such as a polyalkylene Example X Component A: Parts Ricinoleyl alcohol 35 Whiting 100 ,Tributyl phosphate 30 Colloidal silica 10 Barrier C: I

Epoxy ester 30 Whiting 50 Component B:

Prepolymer of urethane 100 Whiting 50 Colloidal silica 15 Plasticizer (e.g. chlorinated biphenyls) 20 more barriers.

polysulfide adapted to form a rubber-like material (e.g. Thiokol LP-32" Of the Thiokol Chemical Corp.) is compounded with pigments in the proportions shown and introduced into the container. A barrier composition is addedbyithe two-step process described in Example VII. The'lead-dioxide activator in dibutyl phthalate plasticizer -is then added to the container above the hardened bar- .Piccopale resin, epoxy ester, and terpene polymers. 20 i In some instances it will be desirable to arrange the components according to viscosity rather than density. This will be true with two-component systems as well as with multi-component systems incorporating two or An example of such multi-component chemical system, comprising three reactive components and two barrier layers therebetween as'shown in Fig. 2, is given below.

' Example XII Parts Component A:

Tertiary amine -c 40 Barrier C:

Chlorinated biphenyls 20 Component A":

Polyalkylene polysulfide Colloidal silica 20 Calcium carbonate 50 Barrier C":

Chlorinated wax 20 Component B:

Epoxy resin 130 Colloidal silica 20 Calcium carbonate 50 Component B, comprising an intimate mixture of a liquid epoxy resin, as described in Example -I, with colloidal silica and calcium carbonate, which serve as pigments and extenders, is introduced into the container as the first, most viscous component. A barrier layer C of chlorinated wax, having a viscosity ranging from 20 poises to solidat normal room temperature, is then deposited on top of component B, to receive the second reactive component A".. Polyalkylene polysufides, including one or more of the polymers produced by the chemical reaction between dichlorodiethylformal and an alkali polysulfide, as liquid polymers, water-dispersed latices and emulsions, organic polysulfide rubbers. and related forms, and particularly the Thiokol products mareted under the designations LP-2, LP-32, LP-3, LP-33 and LP-8, are admixed with colloidal silica and calcium carbonate to form a layer of component A" on top of barrier C". Thiokol LP- -32, typical of the liquid polymers, has a specific gravity of 1.27 at 20 C., an average molecular weight of 4000, an open-cup flash point of approximately 230 C. and a viscosity of 350 to 450 poises at 25 C. A second barrier C, comprising chlorinated biphenyls of the type marketed under the trade name of Arochlor 1254, 1258, 1260 and 1262 and having respective chlorine contents of 54%, 58%, 60% and 62%, is deposited above thelayer of component A". These chlorinated biphenyls have been described in Example IV. The final'reactive component A, to be introduced into the one-package system above the barrier C, comprises a tertiary-amine activator for the components A" and B. Component A may include a sub-' stituted aminomethylphenol of the type marketed under the name DMP 10 by Rohmv and Haas Co.

Since the barrier composition is selected to impart desired properties to the finished mix (e.g. as in Example I wherein it acts as a plasticizer, fire-retarder .and lowcost filler), it will be apparent that the compositions may be altered, proportions changed and compounds interchanged or added as required for -a particular purpose. The invention may readily be seen to extend to many reaction systems, not described, known to persons skilled in the art and intended to be included within the spirit and scope of the invention except as further limited by the appended claims.

I claim:

1. A packaging unit comprising a container, a first and a second component in said container capable of interacting with each other, and a barrier layer separating said components, said layer consisting at least in part of a material foreign to said components but compatible with their interaction product.

2. A unit according to claim 1 wherein said layer is solid.

3. A unit according to claim 2 wherein said layer consists to a major extent of wax.

4. A unit according to claim 1 wherein said layer contains a colorant for said interaction product.

5. A unit according to claim 1 wherein said layer contains a fire-retarding agent for said interaction product.

6. A packaging unitcomprising a container, a lower and an upper component in said container capable of interacting with each other, and ahorizontal barrier layer separating said components, said layer consisting at least in part of a material foreign to said components but compatible with their interaction product.

7. A unit according to claim 6 wherein said lower component has a density greater than that of said upper component.

8. A unit according to claim 7 whereintsaid barrier layer is a liquid having.adensityintermediate the densities of said components.

9. A unit according to claim 8 whereina major proportionof said barrierlayer consists of a non-drying alkyd.

10. A unit according to claim 6 wherein said layer contains a thixotropic substance as a major ingredient.

11. A unit according to claim 10 wherein said thixotropic substance ispetroleum jelly.

12. A packaging unit comprising a container, a first and a second component in said container capable of combining with each other in an exothermic reaction, and a substantially solid barrier layer separating said components, said layer being liquefiable by the exothermic reaction and compatible with the reaction product formed thereby.

13. A unit according to claim 12 wherein said layer consists to a major extent of a mixture of microcrystalline and halogenated waxes.

14. A packaging unit comprising -a container, a polymerizable organic compound in said container, a polymerization promoter in said container, and a barrier layer separating said compound from said promoter, said barrier layer consisting of a material compatible with the polymerized compound.

15. A unit according to claim-14 wherein said barrier layer contains a polymerization-retarding agent.

16. A process for packaging two components capable of interacting with each other, comprising the steps of introducing one of said components into .a container, topping said one component with a barrier layer of a material compatible with the interaction product of said components, depositing on said layer the other of said :components, storing the container so charged, :and sub- .container so charged, and subsequently initiating interaction of said components by stirring the contents of said container into a mixture.

19. A process for packaging two components capable of exothermally interacting with each other, comprising the steps of introducing one of said components into a container, liquefying a barrier material which is substantially solid at ambient temperatures and compatible with the interaction product of said components, introducing the so liquefied material into the container as a separating layer overlying said one component, allowing said layer to solidify, depositing on the so solidified layer the other of said components, storing the container so charged, subsequently heating the container sufiiciently to liquefy said layer, and initiating interaction of said components by stirringthe contents of said container into a mixture.

20. A process according to claim 19 wherein said barrier material is introduced into the container in stages, -a part of theliquefied material being added after solidification of a previously deposited portion.

21. A process for packaging two components of different viscosities capable of interacting witheach other,

comprising the steps ofintroducingthe more viscous one of saidcomponents into a container, topping said more viscouscomponent with a barrier layer of a material compatible with the interaction product of said components, depositingon said layer the other of said components, storing the container so charged, and subsequently initiating interaction of said components by stirring the contents of said container into a mixture.

22. A. packaging unit comprising a container, three components in said container capable of interacting with each other, a barrier layer separating one of said components from a second of said components, and another barrier layer separating the third component from said second of said components.

23. A packaging unitcomprising a container, a first component consisting in major part of a polyalkylene V polysulfide, a second component consisting in major part of a compound adapted to react with and cure said polyalkylene polysulfide in said container, and a barrier layer separating said components, said layer consisting at least in part of a material foreign to said components but compatible with their interaction products.

24. A packaging unit comprising a container, a first component consisting in major part of an epoxy resin, at second component consisting in major part of a compound adapted to react with and cure said epoxy resin in said container, and a barrier layer separating said com- :ponents, said. layer consisting at least in part of a material foreign to said components but compatible with their I interaction products.

References Cited in the file of this patent UNITED STATES PATENTS 1,846,052 Grant Feb. 23, 1932 

